Carbon disulphide reaction products and process of making same



Patented Oct. 2, 1934 PATENT, OFFICE;

CARBON DISULPHIDE REACTION PRODUCTS AND PROCESS OF MAKING SAME Donald H.Powers, Pennsgrove, N. J., assignor to E. I. du Pont de Nemours &Company, Wilmlngton, Del., a. corporation of Delaware N Drawing. AppliSerial No. 374,292

22 Claims.

This invention relates to a new class of products and the process ofpreparing the same. More specifically, it relates to a class ofcompounds resulting from the interaction of acetaldehyde, primaryaromatic or aliphatic amines resulting from theinteraction of analdehyde, 2. primary amine and carbon disulphide and is moreparticularly directed to such products when obtained from aliphaticaldehydes and aliphatic amines in general. Applications Serial No.140-,- 692 and Serial No. 140,693 aredirected to the :productsobtained-from aldehydes containing a plurality of carbon atoms, primaryamines and carbon disulphide and more specifically are directed to theproducts obtained from aniline, butyraldehyde, and carbon disulphide.

It has been new discovered that the products resulting from thecondensation of acetaldehyde, primary aromatic or aliphatic amines andcarbon disulphide are of peculiar value in a number of commercialapplications, among which may be mentioned their use as inhibitors ofacid corrosion and as accelerators for the vulcanization of rubber. V

The preparation of the new class of compounds may be best disclosed bythe presentation of a number of examples. these examples are purelyillustrative and that the conditions, reagents, and proportions thereinspecified are susceptible of variation.

The examples follow:

Example 1 2 moles'of aniline are added slowly to 2 moles ofacetaldehyde, held at 42-43 0; over a period of minutes. The mixture isheld 2 hours at C. then steam distilled to remove unreactedaniline.2.6'rr'1oles of carbon disulphide are then added and the mixturerefluxed 10 hours at 50 C. The product is dried in vacuoat C.

Example 2 2' moles of acetaldehyde are added to 1 mole 'pf carbondisulphide and the mixture cooled in an ice bath. 2 moles of aniline areadded slowly, with agitation. The mass soon solidifies. It is heated upto about 'C. and" then allowed to solidify.

It is to be understood thatv cation June 27, 1929,-.-

I 'Example3 p I 1 mole of aniline is mixed with 1 mole of carbondisulphide, the temperature being held at or below 40 C. during themixing, and for an additional 30 minutes with agitation. 3 moles ofacetaldehyde are then added with stirring and the temperature is allowedto rise gradually to 60 to The mixture, of aniline and carbon disulphideis held at low temperature in order to avoid the formation ofthio-carbanilid, which would take place at higher temperatures, with theliberation of hydrogen sulphide. I

Example 4 m 1 mole of aniline, 1 mole of acetaldehyde and 3 moles ofcarbon disulphide are added simultaneously to a container, the materialsas they mix in this container being cooled to about 35 C. during theaddition. The mixture is then heated gradually to 70 C. and held therefor 2 hours. The product is then heated under vacuum to distill 01f theexcess carbon disulphide and any other volatile substances.

Example 5 1 mole of butyl amine is mixed with 1 mole of acetaldehyde andthe mixture is stirred for 40 minutes at a temperature of approximately45 C. The temperature is then raised'to 55 C. and held 2 hours. 1L3moles of carbon disulphide are then'added and the mixture is refluxedfor 12 hours. Theproductis then heatedin vacuo to remove volatileproducts.

It will be understood that butyl amine in the above example is onlyillustrative of the use of an aliphatic amine and that other primaryaliphatic amines may be used to form products of this kind, such forexample as propyl amine, amyl amine, etc.

It will be obvious from the above examples that the proportions of thethree components employed may bewidely varied. vThus, valuable productshave been obtained when from 1 to 3 or even more than 3 moles of carbondisulphide are employed for each mole of amine. -Moreover, the quantityof acetaldehyde to amine may be varied within wide limits. Thus,valuable products have been obtained by using anywhere from 1 to 5m'olesof acetaldehyde to 1 mole of amine. The invention therefore is notlimited to specific proportions of the reagents. However, in thepreferred embodiment of the invention substantially equal molecularproportions of amline, acetaldehyde and carbon disulphide are reacted,although it is often advisable to use a slight excess of carbondisulphide to allow for losses during the reaction.

The products of the invention are very high boiling, viscous liquids,dark in color and with a characteristic odor. 'An increase in theproportion of aldehyde employed results in certain changes inproperties. When the products,.for example, are used as accelerators, anincreasein the aldehyde up to a certaingpoint zincreasestheii activity.With increasing aldehyde the products also tend to become less solublein acid, and therefore less valuable as :ac'id "inhibitors. An increasein the proportion of narbon bisulphide, of course, results in anincrease in the amount of combined sulphur, and therefore (tends toaincrease accelerating activity but to decreasesolubility in acid. All ofthe products, however, exhibit marked ability to inhibit corrosion dueto the action of non-oxidizing acids, such as sulphuric and hydrochloricacids on metals and all are elrec'tive accelerators for thevulcanization of rubber.

Itwill also *be obvious from the above examples that the reagents may bebrought together in various ways. Thus, the acetaldehyde, amine andcarbon disulphide may be introduced into the vessel at substantially thesame time; the acetaldehyde and amine may be first reactedand theresu'lting product treated-with the'carbon disulphide; the-amineandcarbon disulphide may befirst introducedinto the vessel and when thereaction is completed the product treated with the acetaldehyde; or,finally, the acetaldehyde and carbon disulphide may be first mixedtogetheraand the :amine thereafter introduced into the mixture.

:Further, it .will be obvious from the examples thQtLGithBl' zprimar-yaromatic or aliphaticamines :nrayrbe-zemployed. Obviously,-also, otherprimary .z'amines than :those specifically disclosed in the examples,may 'be i employed. Thus :va'luable compounds .may be :obtained bysubstituting, for example, the toluidines and xyiidines, .for :aniline,and products of valuemayalso be obtained from the naphthylamines.

.The products I obtainedas illustrated in the ex- -.amples .are ofindefinite constitution ibut contain in combination substantiallyall :ofthe elements of the respective reagents with the exception (ofthefieliminationoi water. When amineand-carbondisulphide are admixed thereaction is carried out at low temperatures .and under these conditionshydrogen sulphide is not evolved or, ,at least, .isnot :evolved in :morethan incidental amounts. The production oithioureainsubstantial amounts,which would defeat :the purposes of the invention, is thus avoided.-When aldehyde and famine are first reacted and carbon disulphidethereafter added, hydrogen sulphide iswnot evolved. Y

The ;products of the invention sharply 'diiier :fromthe known productsof 'Delepine-(see Bulle- -tin derla Societe Chemique-de-Paris, 3dSeries, vol; 15, 5p. .898) which :products :are made from .amm'oni-a anddonothave acceleratingiproperties.

As many apparent :and widely, different embodimentspfrthis :inventionmaybe made -.with- 1out -departing-from ithe .spirit thereof it is to be*understood -thatsIzdo-not-limit myself to' -the fore- --going examplesordescription except :as indicated in-theffollowing. claims.

fI'claim: .1. "The ipro'duct "obtained "by .the ccheniical combinationof acetaldehyde, a primary amine and carbon disulphide withoutliberation of substantial quantities of hydrogen sulphide.

2. The product obtained by the chemical combination of acetaldehyde, aprimary aromatic amine and carbon disulphide without liberation ofsubstantial quantities of hydrogen sulphide.

3. The product obtained by the chemical combination, without liberationof substantial quantities of hydrogen sulphide, of acetaldehyde, anilinezand'ca'rbon @disulphide.

A. The product obtained by the chemical combination, without liberationof substantial quantities ofihydrogen' sulphide of from 1 to 5 moles.oiaceta'ldehyde, 13111018 of a primary amine and carbon disulphide.

Thetproduct obtained by the chemical combination, without liberation ofsubstantial quantities of hydrogen sulphide, of from 1 to 5 moles ofacetaldehyde, 1 mole of a primary aromatic .amineiandcarbon disulphide;

6. The product-obtained .byzthe chemical combination, without liberation.of substantial quantities of hydrogen sulphide, of from )1 :to :5 molesof acetaldehyde, ,1 mole of aniline-:and carbon disulphide.

1 ThQlPFOdllCt obtained by :the chemical combination, 7 withoutliberation of substantial quantities of hydrogen sulphide, of 11' mole-.of :a ,pri- .mary aromatic amine, substantially 'l 'mole -;of.acetaldehyde and substantially 1 mole {of-carbon disulphide. '8.Theproduct obtained byathe chemical combination, without liberation ofsubstantial aquari- ,.tities1of-hydrogen sulphide, of :1 :moleof:aniline,

'1 mole-of acetaldehyde-and '1 mole of-carbon disulphide.v V r :9. Theproduct. obtained by reacting from 11 to-5 moles of acetaldehyde ,with 1amole of a :primaryemine .and treating the :product so iformed withcarbon disulphide.

10. The product obtained by reacting from ;1 to 5 moles-ofacetaldehydenwith lmole-of a: primary aromatic amine and treating the;product so formed with carbon-disulphide.

1,1. The product obtained by reacting acetaldehyde with aniline andtreating :the product so formed with carbon disulphide.

-12. The product obtained by :first :reacting :1 .mole of aniline withsubstantially -1:mole.,of acetaldehyde and thereafter treating theresulting product with substantially 1 mole of carbon disulphide. i

13. The process 'of preparing a new :product which comprises reacting,without liberation of substantial quantities of hydrogensulphide,z-acetaldehyde, a primary amine and carbon :disulphide.

14. The process of preparing a new product which comprises reacting,without liberation of substantial quantities of hydrogen sulphide,:acetaldehyde, a primary aromatic amine and carbon disulphide.

15. The process of preparing a new product which comprises reacting,without liberation of substantial quantities of hydrogen 'ssulphide,facetaldehyde, aniline and carbon disulphide.

16. The process of preparing a new product which comprises reacting,without liberation of substantial quantities of hydrogen sulphide, 1mole of a primary amine, substantially '1 :mole of 'acetaldehyde andsubstantially 1 mole ofcarbon disulphide.

17. The process 'of preparing :a new product which comprises reacting,without liberation" of 1 mole of acetaldehyde and thereafter treatingthe resulting product with substantially 1 mole of carbon disulphide.

21. The product obtained by the chemical combination of acetaldehyde, aprimary aliphatic amine andcarbon disulphide without liberation ofsubstantial quantities of hydrogen sulphide.

22. The process of preparing a new product which comprises reacting,without liberation of substantial quantities of hydrogen sulphide, onemole of butyl amine, substantially one mole of acetaldehyde and from 1to 3 moles of carbon disulphide.

DONALD H. POWERS.

